Catalytic hydrodeoxygenation of fast pyrolysis bio-oil of chlorella over Ni-Cu/ZrO<sub>2</sub> catalyst

ZHANG Liang; WU Man; YANG Ya; ZHANG Xiuli; XU Xiufeng; GUO Qingjie

doi:10.3969/j.issn.0438-1157.2014.08.022

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Catalytic hydrodeoxygenation of fast pyrolysis bio-oil of chlorella over Ni-Cu/ZrO₂ catalyst

更新时间：2025-12-10

- Catalytic hydrodeoxygenation of fast pyrolysis bio-oil of chlorella over Ni-Cu/ZrO₂ catalyst
- CIESC Journal Issue 8, Pages: 3004-3011(2014)
- 作者机构：
  
  1. 青岛科技大学化工学院, 清洁化工过程山东省高校重点实验室,山东,青岛,266042
  2. 烟台大学应用催化研究所,山东,烟台,264005
- 作者简介：
- 基金信息：
- DOI：10.3969/j.issn.0438-1157.2014.08.022
  CLC： K6
- Online First：05 August 2014，
  
  Published：05 August 2014
- 稿件说明：
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ZHANG Liang, WU Man, YANG Ya, et al. Catalytic hydrodeoxygenation of fast pyrolysis bio-oil of chlorella over Ni-Cu/ZrO₂ catalyst[J]. CIESC Journal, 2014, (8): 3004-3011. DOI: 10.3969/j.issn.0438-1157.2014.08.022.
DOI：

ZHANG Liang, WU Man, YANG Ya, et al. Catalytic hydrodeoxygenation of fast pyrolysis bio-oil of chlorella over Ni-Cu/ZrO₂ catalyst[J]. CIESC Journal, 2014, (8): 3004-3011. DOI: 10.3969/j.issn.0438-1157.2014.08.022. DOI：

摘要

在小型固定床反应器中以Ni-Cu/ZrO2为催化剂，对小球藻热解油进行催化加氢脱氧，以改善生物油性能。利用XRD、H2-TPR、TG、NH3-TPD等技术对催化剂进行了结构表征。结果表明，Cu的加入有效促进了Ni-Cu/ZrO2催化剂活性相的表面分散，提高了该催化剂对小球藻热解油加氢脱氧反应的催化活性。在2 MPa、350 ℃反应条件下，随Cu/Ni的增大，Ni-Cu/ZrO2的催化活性先升高后降低，Cu/Ni质量比为0.40时的催化性能最好，连续运行3 h后所得精制生物油脱氧率达82.0%。Ni-Cu/ZrO2催化剂在反应过程中，表面结焦少，活性粒子及催化剂性能稳定，连续运行24 h后所得精制生物油脱氧率依然维持在77.0%以上。小球藻热解油经催化加氢脱氧所得的精制生物油，低位热值由31.5 MJ·kg-1提高至35.0 MJ·kg-1，40℃运动黏度由20.5 mm2·s-1降至9.5 mm2·s-1，且油品中水分更易于脱除。精制生物油中高级脂肪酸的含量减少，油品稳定性大幅提高。

Abstract

The catalytic hydrodeoxygenation of bio-oil obtained by fast pyrolysis of chlorella over Ni-Cu/ZrO2 catalyst was carried out in a fixed-bed reactor to improve the quality of the bio-oil. The catalysts were characterized by XRD

H2-TPR

TG and NH3-TPD techniques. The results showed that the addition of Cu promoted dispersion of active species

and increased catalytic hydrodeoxygenation activity of Ni-Cu/ZrO2 catalysts. However

the activity went up first

and then went down with increase of Cu loading. A possible theoretical explanation was also given. At reaction conditions of 2 MPa and 350℃

the performance of Ni-Cu/ZrO2 catalyst was stable and it made the oxygen content in the bio-oil decreased sharply. For the Ni-Cu/ZrO2 catalyst with Cu/Ni mass ratio of 0.40

the efficiency of oxygen removal was 82.0% after 3 h reaction and larger than 77.0% after 24 h reaction. The heat value of upgraded bio-oil increased from 31.5 MJ·kg-1 to 35.0 MJ·kg-1

while the kinetic viscosity at 40℃ fell from 20.5 mm2·s-1 to 9.5 mm2·s-1 after hydrodeoxygenation reaction. In addition

the water in upgraded bio-oil could be removed easily. Furthermore

the stability of upgraded bio-oil was improved significantly due to the reduction of unstable acids.

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Catalytic hydrodeoxygenation of fast pyrolysis bio-oil of chlorella over Ni-Cu/ZrO2 catalyst

DOI：10.3969/j.issn.0438-1157.2014.08.022

摘要

Abstract

关键词

Keywords

references

Catalytic hydrodeoxygenation of fast pyrolysis bio-oil of chlorella over Ni-Cu/ZrO₂ catalyst